EP1578706A2 - Manufacture of trialkylaluminum compounds and alpha-alcohols - Google Patents
Manufacture of trialkylaluminum compounds and alpha-alcoholsInfo
- Publication number
- EP1578706A2 EP1578706A2 EP02790087A EP02790087A EP1578706A2 EP 1578706 A2 EP1578706 A2 EP 1578706A2 EP 02790087 A EP02790087 A EP 02790087A EP 02790087 A EP02790087 A EP 02790087A EP 1578706 A2 EP1578706 A2 EP 1578706A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- bound
- carbon group
- hydrogen
- mixture
- ring atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 58
- 239000001257 hydrogen Substances 0.000 claims abstract description 58
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000004711 α-olefin Substances 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000005977 Ethylene Substances 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000003624 transition metals Chemical class 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 77
- 125000006413 ring segment Chemical group 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 31
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 30
- 238000006384 oligomerization reaction Methods 0.000 claims description 24
- 229910052736 halogen Inorganic materials 0.000 claims description 22
- 150000001336 alkenes Chemical class 0.000 claims description 17
- 125000000524 functional group Chemical group 0.000 claims description 15
- 150000002431 hydrogen Chemical group 0.000 claims description 11
- 125000003107 substituted aryl group Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 150000002367 halogens Chemical group 0.000 claims description 8
- NALBLJLOBICXRH-UHFFFAOYSA-N dinitrogen monohydride Chemical compound N=[N] NALBLJLOBICXRH-UHFFFAOYSA-N 0.000 claims description 6
- 150000004698 iron complex Chemical class 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- PMWXGSWIOOVHEQ-UHFFFAOYSA-N pyridine-2,6-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=N1 PMWXGSWIOOVHEQ-UHFFFAOYSA-N 0.000 claims description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims 1
- 229910000071 diazene Inorganic materials 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 abstract description 11
- 230000003606 oligomerizing effect Effects 0.000 abstract description 4
- 239000000543 intermediate Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 18
- 125000005843 halogen group Chemical group 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 14
- 125000003118 aryl group Chemical group 0.000 description 11
- 125000004429 atom Chemical group 0.000 description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 10
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 125000004953 trihalomethyl group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- -1 1-adamantyl Chemical group 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000002483 hydrogen compounds Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000006519 CCH3 Chemical group 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010959 commercial synthesis reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- QIUBLANJVAOHHY-UHFFFAOYSA-N hydrogen isocyanide Chemical group [NH+]#[C-] QIUBLANJVAOHHY-UHFFFAOYSA-N 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
- C07C29/54—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only starting from compounds containing carbon-to-metal bonds and followed by conversion of the -O- metal to -OH groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/062—Al linked exclusively to C
Definitions
- ⁇ -Olefins are manufactured by oligomerizing ethylene using a transition metal containing catalyst, the ⁇ -olefins are converted to trialkylaluminum compounds by contacting them with aluminum and hydrogen with heat and pressure. The trialkylaluminum compounds which are formed may be reacted with oxygen to form the corresponding trialkoxyaluminum compounds, which can be hydrolyzed to form ⁇ - alcohols.
- HTAC TECHNICAL BACKGROUND Higher trialkylaluminum compounds
- R 3 3 AI in which the alkyl groups contain more than 4 carbon atoms, are useful particularly as chemical intermediates for the synthesis of ⁇ -alcohols of the formula 32 R 33cHCH 2 OH (II) wherein R 3 is hydrogen or alkyl and R 33 is alkyl.
- ⁇ -Alcohols containing 10 to 20 carbon atoms are useful as intermediates for the synthesis of detergents and other surfactants. Therefore improved methods of making (I) and/or (II) are commercial interest.
- linear ⁇ -alcohols are often made utilizing the following steps, see for instance B.
- Triethylaluminum is produced by contacting under relatively high pressure and temperature a mixture of aluminum, hydrogen, ethylene and triethylaluminum (TEA). "New" TEA is produced in the reactor. The liquid product is removed from the reactor, filtered and some is recycled back to the TEA reactor and some is used in the next step.
- the product of the previous step is mixed with oxygen (a highly exothermic reaction) to form the corresponding trialkoxyaluminum compounds.
- the trialkoxyaluminum compounds are hydrolyzed to form an alpha-alcohol mixture and alumina.
- This invention concerns, a process for the manufacture of higher trialkylaluminum compounds, comprising, forming an ⁇ -olefin or mixture of ⁇ -olefins by oligomerization of ethylene using a transition metal containing oligomerization catalyst system, then contacting said ⁇ -olefin or said mixture of ⁇ -olefins with aluminum metal, hydrogen and a trialkylaluminum compound at a sufficient temperature and pressure, for a sufficient amount of time, to form a higher trialkylaluminum compound.
- This invention also concerns a process for the manufacture of ⁇ - alcohols, comprising:
- HTAC higher trialkylaluminum compound
- R 31 3 AI AI
- each of R 31 contains 4 or more carbon atoms, preferably 6 or more carbon atoms
- each R 1 is independently R 32 R 33 CHCH 2 - wherein R 32 is hydrogen or alkyl, R 33 is alkyl, and each R 31 contains an even number of carbon atoms.
- R 32 is hydrogen and/or R 33 is n-alkyl.
- the HTAC may contain impurities such as hydrogen bound to aluminum or alkyl groups having less than 4 carbon atoms bound to aluminum, but at least 50 mole percent, more preferably at least 75 mole percent, and especially preferably at least 90 mole percent of the groups bound to aluminum are R 31 -.
- HTAC higher trialkoxyaluminum compound
- R 31 O 3 AI
- each of R 31 contains 4 or more carbon atoms, preferably 6 or more carbon atoms
- each R 31 is independently R 32 R 33 CHCH2- wherein R 32 is hydrogen or alkyl, R 33 is alkyl, and each R 31 contains an even number of carbon atoms.
- R 32 is hydrogen and/or R 33 is n-alkyl.
- R 32 is hydrogen and/or R 33 is n-alkyl.
- a transition metal containing ethylene oligomerization catalyst is meant a catalyst system which contains an element of Groups 3-12 (IUPAC notation) in the catalyst system, and which is capable of oligomerizing ethylene to an ⁇ -olefin.
- Transition metal containing "inert" supports are not considered part of the catalyst system. By “inert” in this context is meant that the support is believed to function merely as a physical support and does not actually take part chemically in the oligomerization process.
- Transition metal containing catalysts that oligomerize ethylene to ⁇ - olefins may be divided into two classes, those that produce a mixture of ⁇ - olefins and those that produce (mostly) a single ⁇ -olefin.
- the former are exemplified by those catalysts found in U.S. Patents 6,103,946, 2,787,626, 3,032,574, 3,207,770, 3,644,564, 3,647,915 and 3,647,915, all of which are hereby included by reference.
- These oligomerizations herein may be run under conditions described in these references and in other references for other such types of catalysts.
- these catalysts produce a homologous series of ⁇ -olefins that differ by two carbon atoms.
- the amounts of each olefin in the homologous series typically follow a so- called Schulz-Flory distribution, which uses a factor K from the Schulz- Flory theory (see for instance B. Elvers, et al., Ed. Ullmann's Encyclopedia of Industrial Chemistry, Vol. A13, VCH Verlagsgesellschaft mbH,
- K n(C n+2 olefin)/n(C n olefin) wherein n(C n olefin) is the number of moles of olefin containing n carbon atoms, and n(C n+2 olefin) is the number of moles of olefin containing n+2 carbon atoms, or in other words the next higher oligomer of C n olefin. From this can be determined the weight (mass) fractions of the various olefins in the resulting oligomeric reaction product mixture.
- the K factor is preferred to be in the range of about 0.6 to about 0.8
- a preferred type of ethylene oligomerization catalyst is described in
- Such a preferred active ethylene oligomerization catalyst comprises an iron complex of a compound of the formula
- R 1 , R 2 and R 3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group, provided that any two of R 1 , R 2 and R 3 vicinal to one another taken together may form a ring;
- R 4 and R 5 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group
- R 6 and R 7 are each independently a substituted aryl having a first ring atom bound to the imino nitrogen, provided that: in R 6 , a second ring atom adjacent to said first ring atom is bound to a halogen, a primary carbon group, a secondary carbon group or a tertiary carbon group; and further provided that in R 6 , when said second ring atom is bound to a halogen or a primary carbon group, none, one or two of the other ring atoms in R 6 and R 7 adjacent to said first ring atom are bound to a halogen or a primary carbon group, with the remainder of the ring atoms adjacent to said first ring atom being bound to a hydrogen atom; or in R 6 , when said second ring atom is bound to a secondary carbon group, none, one or two of the other ring atoms in R 6 and R 7 adjacent to said first ring atom are bound to a halogen, a primary carbon group or a secondary carbon group
- hydrocarbyl group is a univalent group containing only carbon and hydrogen.
- hydrocarbyls may be mentioned unsubstituted alkyls, cycloalkyls and aryls. If not otherwise stated, it is preferred that hydrocarbyl groups (and alkyl groups) herein contain 1 to about 30 carbon atoms.
- substituted hydrocarbyl herein is meant a hydrocarbyl group that contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected (e.g., an inert functional group, see below).
- the substituent groups also do not substantially detrimentally interfere with the oligomerization process or operation of the oligomerization catalyst system.
- substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of "substituted” are rings containing one or more heteroatoms, such as nitrogen, oxygen and/or sulfur. In a substituted hydrocarbyl, all of the hydrogens may be substituted, as in trifluoromethyl.
- (inert) functional group herein is meant a group, other than hydrocarbyl or substituted hydrocarbyl, which is inert under the process conditions to which the compound containing the group is subjected.
- the functional groups also do not substantially deleteriously interfere with any process described herein that the compound in which they are present may take part in.
- Examples of functional groups include halo (fluoro, chloro, bromo and iodo), and ether such as -OR 50 wherein R 50 is hydrocarbyl or substituted hydrocarbyl.
- the functional group alone should not coordinate to the metal atom more strongly than the groups in those compounds that are shown as coordinating to the metal atom, that is they should not displace the desired coordinating group.
- a “primary carbon group” herein is meant a group of the formula -CH 2 — , wherein the free valence — is to any other atom, and the bond represented by the solid line is to a ring atom of a substituted aryl to which the primary carbon group is attached.
- the free valence — may be bonded to a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a sulfur atom, etc.
- the free valence — may be to hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group.
- Examples of primary carbon groups include -CH 3 , -CH 2 CH(CH 3 ) 2 , -CH 2 CI, -CH 2 C 6 H 5 , -OCH 3 and -CH 2 OCH 3 .
- a secondary carbon group is meant the group
- both free bonds represented by the dashed lines are to an atom or atoms other than hydrogen.
- These atoms or groups may be the same or different.
- the free valences represented by the dashed lines may be hydrocarbyl, substituted hydrocarbyl or inert functional groups.
- a "tertiary carbon group” is meant a group of the formula
- the bond represented by the solid line is to a ring atom of a substituted aryl to which the tertiary carbon group is attached, and the three free bonds represented by the dashed lines are to an atom or atoms other than hydrogen.
- the bonds represented by the dashed lines are to hydrocarbyl, substituted hydrocarbyl or inert functional groups.
- aryl is meant a monovalent aromatic group in which the free valence is to the carbon atom of an aromatic ring.
- An aryl may have one or more aromatic rings which may be fused, connected by single bonds or other groups.
- substituted aryl is meant a monovalent aromatic group substituted as set forth in the above definition of “substituted hydrocarbyl”. Similar to an aryl, a substituted aryl may have one or more aromatic rings which may be fused, connected by single bonds or other groups; however, when the substituted aryl has a heteroaromatic ring, the free valence in the substituted aryl group can be to a heteroatom (such as nitrogen) of the heteroaromatic ring instead of a carbon.
- first ring atom in R 6 and R 7 bound to an imino nitrogen atom is meant the ring atom in these groups bound to an imino nitrogen shown in (I), for example
- R 6 is
- R 8 is a halogen, a primary carbon group, a secondary carbon group or a tertiary carbon group
- R 9 , R 10 , R 11 , R 14 , R 15 , R 16 and R 17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group; provided that: when R 8 is a halogen or primary carbon group none, one or two of R 12 , R 13 and R 17 are a halogen or a primary carbon group, with the remainder of R 12 , R 13 and R 17 being hydrogen; or when R 8 is a secondary carbon group, none or one of R 12 , R 13 and R 17 is a halogen, a primary carbon group or a secondary carbon group, with the remainder of R 12 , R 13 and R 17 being hydrogen; or when R 8 is a tertiary carbon group, none or one of R 12 , R 13 and R 17 is tertiary carbon group, with the remainder of R 12 , R 13 and R 17 being hydrogen; and further provided that any two of R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 ,
- R 15 , R 16 and R 17 vicinal to one another, taken together may form a ring.
- R 8 corresponds to the second ring atom adjacent to the first ring atom bound to the imino nitrogen
- R 12 , R 13 and R 17 correspond to the other ring atoms adjacent to the first ring atom.
- R 8 is a primary carbon group, R 13 is a primary carbon group, and R 12 and R 17 are hydrogen; or if R 8 is a secondary carbon group, R 13 is a primary carbon group or a secondary carbon group, more preferably a secondary carbon group, and R 12 and R 17 are hydrogen; or if R 8 is a tertiary carbon group (more preferably a trihalo tertiary carbon group such as a trihalomethyl), R 13 is a tertiary carbon group (more preferably a trihalotertiary group such as a trihalomethyl), and R 12 and R 17 are hydrogen; or if R 8 is a halogen, R 13 is a halogen, and R 12 and R 17 are hydrogen.
- R 1 , R 2 and R 3 are hydrogen; and/or R 4 and R 5 are methyl. It is further preferred that:
- R 9 , R 10 , R 11 , R 12 , R 14 , R 15 , R 16 and R 17 are all hydrogen;
- R 13 is methyl; and
- R 8 is a primary carbon group, more preferably methyl; or
- R 9 , R 10 , R 11 , R 12 , R 14 , R 15 , R 1 ⁇ and R 17 are all hydrogen;
- R 13 is ethyl; and
- R 8 is a primary carbon group, more preferably ethyl; or
- R 10 , R 11 , R 12 , R 14 , R 15 , R 16 and R 17 are all hydrogen;
- R 13 is isopropyl; and
- R 8 is a primary carbon group, more preferably isopropyl; or
- R 9 , R 10 , R 11 , R 12 , R 14 , R 15 , R 16 and R 17 are all hydrogen;
- R 13 is n- propyl; and R 8 is a primary carbon group, more preferably n-propyl; or
- R 9 , R 10 , R 11 , R 12 , R 14 , R 15 , R 16 and R 17 are all hydrogen;
- R 13 is chloro; and
- R 8 is a halogen, more preferably chloro; or
- R 9 , R 10 , R 11 , R 12 , R 14 , R 15 , R 16 and R 17 are all hydrogen;
- R 13 is trihalomethyl, more preferably trifluoromethyl; and
- R 8 is a trihalomethyl, more preferably trifluoromethyl.
- R 6 and R 7 are, respectively
- R 18 is a halogen, a primary carbon group, a secondary carbon group or a tertiary carbon group
- R 19 , R 20 , R 23 and R 24 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group; Provided that: when R 18 is a halogen or primary carbon group none, one or two of R 21 , R 22 and R 25 are a halogen or a primary carbon group, with the remainder of R 21 , R 22 and R 25 being hydrogen; or when R 18 is a secondary carbon group, none or one of R 21 , R 22 and R 25 is a halogen, a primary carbon group or a secondary carbon group, with the remainder of R 21 , R 22 and R 25 being hydrogen; when R 18 is a tertiary carbon group, none or one of R 2 , R 22 and R 25 is a tertiary carbon group, with the remainder of R 21 , R 22 and R 25 being hydrogen; and further provided that any two of R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 and R 25 vicinal to one another, taken together
- R 18 corresponds to the second ring atom adjacent to the first ring atom bound to the imino nitrogen
- R 21 , R 22 and R 25 correspond to the other ring atoms adjacent to the first ring atom.
- R 2 and R 25 are hydrogen; or if R 18 is a secondary carbon group, R 22 is a primary carbon group or a secondary carbon group, more preferably a secondary carbon group, and R 21 and R 25 are hydrogen; or if R 18 is a tertiary carbon group (more preferably a trihalo tertiary carbon group such as a trihalomethyl), R 22 is a tertiary carbon group (more preferably a trihalotertiary group such as a trihalomethyl), and R 21 and R 25 are hydrogen; or if R 18 is a halogen, R 22 is a halogen, and R 21 and R 25 are hydrogen.
- R 1 , R 2 and R 3 are hydrogen; and/or R 4 and R 5 are methyl. It is further preferred that:
- R 19 , R 20 , R 21 , R 23 and R 24 are all hydrogen; R 22 is methyl; and R 18 is a primary carbon group, more preferably methyl; or R 19 , R 20 , R 21 , R 23 and R 24 are all hydrogen; R 22 is ethyl; and R 18 is a primary carbon group, more preferably ethyl; or
- R 19 , R 20 , R 21 , R 23 and R 24 are all hydrogen; R 22 is isopropyl; and R 18 is a primary carbon group, more preferably isopropyl; or
- R 19 , R 20 , R 21 , R 23 and R 24 are all hydrogen; R 22 is n-propyl; and R 18 is a primary carbon group, more preferably n-propyl; or
- R 19 , R 20 , R 21 , R 23 and R 24 are all hydrogen; R 22 is chloro or bromo; and R 18 is a halogen, more preferably chloro or bromo.
- ethylene olgimerization catalyst is typified by that described in U.S. Patent 5,382,738.
- these types of catalysts produce (predominantly) a single olefin having a relatively low number of carbon atoms, such as 1-hexene or 1-octene.
- These types of catalysts may also be used in the present processes to oligomerize ethylene as described in the references concerning these catalysts.
- an ethylene oligomerization catalyst system that produces a homologous series of ⁇ -olefins be used. It is also preferred that this catalyst system produces a product with a high molar percentage
- the production of the HTAC from hydrogen, aluminum and the ⁇ - olefin(s) can be carried out by methods known in the art, see for instance U.S. Patents 2,787,626, 3,032,574, 3,207,770 and 3,960,912 and W. Gerhartz, et al., Ed., Ullmann's Encyclopedia of Industrial Chemistry, 5 th Ed., Vol. A1 , VCH Veriagsgesellschaft mbH, Weinheim, 1985, p. 545-549, which is hereby included by reference.
- the process may be carried out in a single reactor or in a series of reactors as in U.S. Patent 3,960,912.
- Typical reaction conditions in a single reactor are 70kPa to 20 MPa hydrogen pressure, a temperature of 80°C to 180°C for a period of about 1 hour to about 24 hours. The conditions will be interdependent on each other and also on the starting materials used, particularly the ⁇ -olefin(s) used. Typically also present in these processes is a trialkylaluminum compound.
- HTAC trialkylaluminum compound
- HTAC HTAC or mixtures thereof which are meant to be produced in the process.
- some of the product HTAC will likely be recycled back to the reactor making the HTAC, and some will be taken off as product.
- the ⁇ -olefin(s) from the ethylene oligomerization reaction undergo little or no purification before being put into the process to make the HTAC. If a mixture of ⁇ -olefins are produced they are preferably not separated.
- the ethylene oligomerization catalyst may be deactivated or not (if present it may be deactivated by the usually higher temperatures of the HTAC forming process).
- a solvent may be used in the ethylene oligomerization reaction, and preferably it does not contain active hydrogen compounds such as water, alcohols or carboxylic acids. If the solvent does not contain active hydrogen compounds it does not need to be separated before the reactions to form the HTAC.
- Preferred solvent in the oligomerization reaction are nonolefinic hydrocarbons such as toluene, xylene, octane, cyclohexane, and the like.
- the composition of the HTAC(s) produced will depend on the composition of the ⁇ -olefin (mixture) added to the HTAC forming reaction.
- Reaction of the HTAC(s) with oxygen or other oxidizing agent to form higher trialkoxyaluminum compounds can be carried out as known in the art, see for instance . Elvers, et al., Ed., Ullmann's Encyclopedia of Industrial Chemistry, 5 th Ed., Vol. A28, VCH Veriagsgesellschaft mbH, Weinheim, 1996, p. 505-508 and references therein, and U.S. Patent 5,278,330 which is hereby included by reference.
- hydrolysis of the higher trialkoxyaluminum compound to form ⁇ -alcohols may be carried out by methods known in the literature, see for instance Elvers, et al., Ed., Ullmann's Encyclopedia of Industrial Chemistry, 5 th Ed., Vol. A28, VCH Veriagsgesellschaft mbH, Weinheim, 1996, p. 505-508 and references therein, and U.S. Patent 5,278,330. These methods for oxidation and hydrolysis to form ⁇ -alcohols are known in the art.
- the present process form making the HTAC(s) and/or ⁇ -alcohols result in less handling of pyrophoric alkylaluminum compounds at high temperatures and/or pressure, thereby making the process safer and/or lowering operating cost, and/or lowering investment need for the plant, when compared to the conventional methods of manufacturing these types of compounds.
- the product mixture resulting, for example, from making ⁇ -alcohols may be similar to that obtained with current manufacturing methods.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US34044401P | 2001-12-12 | 2001-12-12 | |
US340444P | 2001-12-12 | ||
PCT/US2002/039636 WO2003053889A2 (en) | 2001-12-12 | 2002-12-12 | Manufacture of trialkylaluminum compounds and alpha-alcohols |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1578706A2 true EP1578706A2 (en) | 2005-09-28 |
EP1578706A4 EP1578706A4 (en) | 2007-08-15 |
EP1578706B1 EP1578706B1 (en) | 2009-01-21 |
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Application Number | Title | Priority Date | Filing Date |
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EP02790087A Expired - Lifetime EP1578706B1 (en) | 2001-12-12 | 2002-12-12 | Manufacture of trialkylaluminum compounds and alpha-alcohols |
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US (1) | US6822108B2 (en) |
EP (1) | EP1578706B1 (en) |
JP (1) | JP2005514395A (en) |
CN (1) | CN1612882A (en) |
AT (1) | ATE421520T1 (en) |
AU (1) | AU2002353112A1 (en) |
DE (1) | DE60231011D1 (en) |
WO (1) | WO2003053889A2 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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DE60204455T2 (en) * | 2001-05-10 | 2006-03-23 | Univation Technologies, LLC, Houston | A POLYMERIZATION OF OLEFINES CONTAINING PYRROLIBISIMINLIGANDS |
KR101579880B1 (en) * | 2012-05-10 | 2016-01-04 | 주식회사 엘지화학 | Process for oligomerization of ethylene |
WO2018043418A1 (en) * | 2016-08-30 | 2018-03-08 | Jxtgエネルギー株式会社 | Method for producing oligomer and catalyst |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US3474122A (en) * | 1965-09-01 | 1969-10-21 | Sumitomo Chemical Co | Process for producing higher alkylaluminums |
US3494948A (en) * | 1965-12-21 | 1970-02-10 | Sumitomo Chemical Co | Process for producing higher alkylaluminums |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
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NL103707C (en) | 1954-02-01 | |||
LU34220A1 (en) | 1955-04-01 | |||
US2787626A (en) | 1955-06-07 | 1957-04-02 | Ethyl Corp | Manufacture of triethylaluminum |
US3487097A (en) * | 1962-10-30 | 1969-12-30 | Ethyl Corp | Process for producing trialkyl aluminum and aluminum trialkoxides |
US3388143A (en) * | 1964-11-23 | 1968-06-11 | Continental Oil Co | Growth reaction |
US3775456A (en) * | 1969-08-04 | 1973-11-27 | Continental Oil Co | Control of distribution of aluminum alkyls and products derived therefrom |
US3644564A (en) | 1969-12-19 | 1972-02-22 | Shell Oil Co | Ethylene oligomerization in the presence of complex nickel-fluorine-containing catalysts |
US3829520A (en) * | 1972-05-15 | 1974-08-13 | Continental Oil Co | Inhibition of olefin isomerization and reverse displacement in catalytic displacement reactions |
DE2361988C3 (en) | 1973-12-13 | 1982-06-16 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Process for the production of aluminum trialkyls |
US4689437A (en) | 1986-07-21 | 1987-08-25 | Union Carbide Corporation | Oligomerization to alpha-olefins |
US5210338A (en) * | 1991-10-25 | 1993-05-11 | Ethyl Corporation | Catalyzed chain growth process |
US5438027A (en) | 1991-12-13 | 1995-08-01 | Phillips Petroleum Company | Chromium compounds and uses thereof |
US5276220A (en) * | 1992-06-18 | 1994-01-04 | Ethyl Corporation | Actinide catalyzed chain growth process |
US5430165A (en) * | 1992-06-29 | 1995-07-04 | Albemarle Corporation | Method of oxidizing aluminum alkyls |
US5233103A (en) * | 1992-06-29 | 1993-08-03 | Ethyl Corporation | Preparation of organoaluminum compounds and linear alcohols derived therefrom |
US5536859A (en) * | 1995-02-27 | 1996-07-16 | Amoco Corporation | Alpha-olefin catalyst and process |
US6103859A (en) * | 1997-04-09 | 2000-08-15 | Eastman Chemical Company | Late addition of supplemental ethylene glycol in the preparation of copolyesters |
US6103946A (en) | 1997-07-15 | 2000-08-15 | E. I. Du Pont De Nemours And Company | Manufacture of α-olefins |
-
2002
- 2002-12-12 EP EP02790087A patent/EP1578706B1/en not_active Expired - Lifetime
- 2002-12-12 DE DE60231011T patent/DE60231011D1/en not_active Expired - Lifetime
- 2002-12-12 WO PCT/US2002/039636 patent/WO2003053889A2/en active Application Filing
- 2002-12-12 AU AU2002353112A patent/AU2002353112A1/en not_active Abandoned
- 2002-12-12 US US10/494,061 patent/US6822108B2/en not_active Expired - Fee Related
- 2002-12-12 JP JP2003554606A patent/JP2005514395A/en active Pending
- 2002-12-12 AT AT02790087T patent/ATE421520T1/en not_active IP Right Cessation
- 2002-12-12 CN CNA028250184A patent/CN1612882A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US3474122A (en) * | 1965-09-01 | 1969-10-21 | Sumitomo Chemical Co | Process for producing higher alkylaluminums |
US3494948A (en) * | 1965-12-21 | 1970-02-10 | Sumitomo Chemical Co | Process for producing higher alkylaluminums |
Non-Patent Citations (1)
Title |
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See also references of WO03053889A2 * |
Also Published As
Publication number | Publication date |
---|---|
AU2002353112A1 (en) | 2003-07-09 |
CN1612882A (en) | 2005-05-04 |
DE60231011D1 (en) | 2009-03-12 |
EP1578706A4 (en) | 2007-08-15 |
US6822108B2 (en) | 2004-11-23 |
EP1578706B1 (en) | 2009-01-21 |
JP2005514395A (en) | 2005-05-19 |
WO2003053889A3 (en) | 2006-09-21 |
WO2003053889A2 (en) | 2003-07-03 |
US20040210073A1 (en) | 2004-10-21 |
AU2002353112A8 (en) | 2003-07-09 |
ATE421520T1 (en) | 2009-02-15 |
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